CN105873894A - Alkali metal salt of perfluoro(vinyloxy polyether) carboxylic acid, and method for producing same - Google Patents
Alkali metal salt of perfluoro(vinyloxy polyether) carboxylic acid, and method for producing same Download PDFInfo
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- CN105873894A CN105873894A CN201480072771.XA CN201480072771A CN105873894A CN 105873894 A CN105873894 A CN 105873894A CN 201480072771 A CN201480072771 A CN 201480072771A CN 105873894 A CN105873894 A CN 105873894A
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C59/00—Compounds having carboxyl groups bound to acyclic carbon atoms and containing any of the groups OH, O—metal, —CHO, keto, ether, groups, groups, or groups
- C07C59/40—Unsaturated compounds
- C07C59/58—Unsaturated compounds containing ether groups, groups, groups, or groups
- C07C59/60—Unsaturated compounds containing ether groups, groups, groups, or groups the non-carboxylic part of the ether being unsaturated
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
- C07C51/41—Preparation of salts of carboxylic acids
- C07C51/412—Preparation of salts of carboxylic acids by conversion of the acids, their salts, esters or anhydrides with the same carboxylic acid part
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Abstract
Provided is an alkali metal salt of a perfluoro(vinyl oxypolyether) carboxylic acid, which is represented by the general formula CF2=CF[OCF2CF(CF3)]bO(CF2)aO[CF(CF3)CF2O]cCF(CF3)COOM [I] (M is an alkali metal, and is preferably sodium or potassium, a is an integer between 1 and 6, and is preferably 2, and the value of b+c is an integer between 0 and 6, and is preferably 0 or 1), wherein the alkali metal salt of a perfluoro(vinyl oxypolyether) carboxylic acid is produced by hydrolyzing or solvolyzing, in the presence of an alkali metal hydroxide, an alkyl ester of a perfluoro(vinyl oxypolyether) carboxylic acid, which is represented by the general formula CF2=CF[OCF2CF(CF3)]bO(CF2)aO[CF(CF3)CF2O]cCF(CF3)COOR [II] (R is an alkyl group having 1-12 carbon atoms, a is an integer between 1 and 6, and the value of b+c is an integer between 0 and 6).
Description
Technical field
The present invention relates to perfluoroethylene epoxide polyether carboxylic acid's alkali metal salt and manufacture method thereof.More specifically, relate to making
The perfluoroethylene epoxide polyether carboxylic acid's alkali used for novel fluorine system reactive emulsifier (there is the emulsifying agent of polymerizable group)
Slaine and manufacture method thereof.
Background technology
Patent documentation 1 describes in the manufacture method of the aqueous liquid dispersion of vinylidene fluoride polymer, shown below
Compound can effectively serve as fluorine system reactive emulsifier, the solid component concentration in described aqueous liquid dispersion is 30 ~ 60 weights
Amount %, described vinylidene fluoride polymer reaches to be suitable as the small particle of the mean diameter of coating, i.e. below 200nm.
Compound 1:F2C=CF(CF2)1~10COOM
Compound 2:F2C=CF(CF2CFX)1~5COOM
Compound 3:F2C=CFO(CF2)1~10COOM
Compound 4:F2C=CFO(CF2CFXO)1~10CF2CFCOOM
Compound 5:H2C=CFCF2O〔CF(CF3)CF2O〕0~10CF(CF3)COOM
Compound 6:F2C=CFCF2O〔CF(CF3)CF2O〕1~10CF(CF3)COOM
X:F or CF3Base
M:H, NH4Or alkali metal.
Compound 1 is by making ω-hydrogen-α, β-dichloro perfluoro alkane high-temperature heating in the presence of chlorine or nitrogen oxides
And the dichloro perfluoro carboxylic acid obtained carries out dechlorination reaction thus synthesizes, not only it is difficult to obtain raw material, and needs at height
Aoxidize under temperature, it may be said that its impracticable (non-patent literature 1).
The manufacture method of compound 4 is recorded in patent documentation 2 in detail, is obtaining the alkoxy carbonyl carbon as initial substance
Acyl chlorides (ROOCCF2COF) employing sulfur trioxide or stannic chloride time, therefore, the secure context at reaction process has problems, separately
Outward, equipment is also required to corrosion resistant apparatus etc., needs special equipment to design.
Compound 5 is as follows is as initiateing using the tetrafluoro oxetanes obtained by the reaction of tetrafluoroethene Yu formaldehyde
Material, and obtain according to route shown below, due to operation length, use use metallic zinc in fluohydric acid gas, the dehalogenation reaction, therefore also
The problem that there is garbage, industrial cannot saying is favourable (patent documentation 3).
About compound 6 CF2=CFCF2OCF(CF3)CF2OCF(CF3) COOH, its detailed manufacture method is still not clear.
It addition, recorded the method obtaining carboxylic acid ammonium, alkali metal carboxylates via carboxylic acid in patent documentation 3, but perfluoroalkyl vinyl ether
Also can be polymerized in the presence of the acid of carboxylic acid degree, mostly become polymer, therefore cause the reduction of yield, in a word, no
The method being suitable as obtaining carboxylic metallic salt.
Prior art literature
Patent documentation
Patent documentation 1: No. 3298321 publications of Japanese Patent No.
Patent documentation 2: Japanese Patent Publication 60-49176 publication
Patent documentation 3: No. 3291733 publications of Japanese Patent No.
Patent documentation 4: Japanese Patent Publication 3-80145 publication
Patent documentation 5: No. 4,617,833 publications of Japanese Patent No.
Non-patent literature
Non-patent literature 1:Zhurnal Organicheskoi Khimll, 16 (3), 540-3 page (1980)
Non-patent literature 2:Fluorine Chem. volume 75 page 163 ~ 167 (1995).
Summary of the invention
The problem that invention is to be solved
It is an object of the invention to, it is provided that without use special equipment, using the raw material that can easily obtain as initial substance,
Can be used as new compound and the manufacture method thereof of fluorine system reactive emulsifier.
Means for solving the above
Pass through the present invention, it is provided that formula CF2=CF〔OCF2CF(CF3)〕bO(CF2)aO〔CF(CF3)CF2O〕cCF(CF3)COOM 〔I〕
Shown perfluoroethylene epoxide polyether carboxylic acid's alkali metal salt, (herein, M is alkali metal, and a is the integer of 1 ~ 6, is preferably 2, and b+c is
The integer of 0 ~ 6, it is preferably 0 or 1), described perfluoroethylene epoxide polyether carboxylic acid's alkali metal salt is by by formula CF2=CF
〔OCF2CF(CF3)〕bO(CF2)aO〔CF(CF3)CF2O〕cCF(CF3) the perfluoroethylene epoxide polyether carboxylic acid shown in COOR (II)
Arrcostab be hydrolyzed in the presence of an alkali metal hydroxide or solvolysis and manufacture, (herein, R be carbon number 1 ~
The alkyl of 12, a is the integer of 1 ~ 6, and b+c is the integer of 0 ~ 6).
The effect of invention
Perfluoroethylene epoxide polyether carboxylic acid's alkali metal salt of the present invention is without special equipment, former with can easily obtain
Material is as initial substance, and gained compound is the new compound that can be used as fluorine system reactive emulsifier, therefore, and can be effective
Ground is for the antireflection film of the cross-linking agent of various polymer, modification agent, display etc., the clad material of optical fiber, bonding agent, various
In the purposes widely such as demoulding coating agent, surface application agent, surface modifier, water-repellent oil-repellent agent.
Detailed description of the invention
Perfluoroethylene epoxide polyether carboxylic acid's alkali metal salt shown in formula (I) is by by the perfluor second shown in formula (II)
Alkenyloxy group polyether carboxylic acid's Arrcostab be hydrolyzed in the presence of an alkali metal hydroxide or solvolysis and manufacture.
As the manufacturing raw material of this reaction, perfluoroethylene epoxide polyether carboxylic acid's Arrcostab (II) that uses is to lead to by making
Formula ROOCCF (CF3)〔OCF2CF(CF3)〕bO(CF2)aO〔CF(CF3)CF2O〕cCF(CF3) perfluor shown in COOR (III) gathers
Ether dicarboxylic acid dialkyl esters and sodium carbonate, potassium carbonate etc. react and carry out vinylated to an end group thus manufacture
(patent documentation 4, non-patent literature 2).This PFPE dicarboxylic acid dialkyl esters (III) is by making formula FOCCF (CF3)
〔OCF2CF(CF3)〕bO(CF2)aO〔CF(CF3)CF2O〕cCF(CF3) the PFPE dicarboxylic acids fluoride shown in COF (IV) exists
React in the presence of the metal fluorides such as the aliphatic alcohol of the carbon number 1 ~ 12 shown in general formula R OH and sodium fluoride and manufacture
(patent documentation 5).
The hydrolysis of perfluoroethylene epoxide polyether carboxylic acid's Arrcostab (II) or solvolysis are in the existence of alkali metal hydroxide
Under carry out, preferably carry out under the reaction temperature of about-20 ~ 0 DEG C.As alkali metal hydroxide, sodium hydroxide, hydrogen are preferably used
Potassium oxide, it is contemplated that the reactivity (surface active ability) etc. in polymerization process suitably selects.They are molten with aqueous solution or alcohol
The form of liquid uses, and as alcohol, can use without particular limitation as long as making alkali metal hydroxide dissolve, from treatability,
From the viewpoint of price, secure context, the aliphatic alcohol of carbon number 1 ~ 6 is preferably used, particularly preferably uses ethanol, isopropyl
Alcohol.It addition, as alcohol, it is possible to use methanol, ethanol, the mixture of isopropanol.Herein, reaction temperature is made less than this
During reaction temperature, the carrying out of reaction can be slack-off, on the other hand, excessive decomposition can occur under high temperature.
The concentration of alkali metal hydroxide aqueous solution or alcoholic solution is not particularly limited, and examines from the application aspect of solution
Consider, preferably use with the concentration of about 10 ~ 20 weight %.In the case of subtle solution, the quantity of reaction solution increases, and sends out
The raw maximization of reaction vessel, the increase etc. of waste liquid, on the other hand, in the case of highly concentrated solution, analyse because of reactant sometimes
Go out and stir bad etc..Alkali metal hydroxide be 0.95 ~ 1.05 times mole relative to carboxylate, be preferably 0.95 ~
The ratio of 1.02 times moles uses.When using alkali metal hydroxide with ratio more than aforementioned proportion, occasionally result in excessively
Decompose.
As the step of reaction, preferably by dripping alkali metal hydrogen in the water-based emulsion (suspension) of ester or in alcoholic solution
The aqueous solution of oxide or alcoholic solution carry out rather than drip ester in alkali hydroxide soln.It addition, it is unreacted
Carboxylate is together recovered with water or alcohol in enrichment process, directly recycles with the form of suspension, alcoholic solution, or from outstanding
Supernatant liquid, alcoholic solution separate generation by distillation, thus recycles.
The drying equipments such as gained reactant mixture Rotary Evaporators, cone drier concentrate, but in uniform temperature
Can carry out decarburization acid decomposition reaction time above, yield reduces, it is therefore preferable that under reduced pressure carry out less than 120 DEG C dry.
Perfluoroethylene epoxide polyether carboxylic acid's alkali metal salt of the present invention is at the emulsion polymerization of such as fluorochemical monomer
Shi Zuowei emulsifying agent and work, additionally it is possible under conditions of reduce the emulsifying agent used or do not use emulsifying agent in the past, carry out breast
Liquid is polymerized.It addition, will also become copolymer composition, it is possible to realize high bonding by Vulcanization etc..
As carrying out the fluorochemical monomer of emulsion polymerization in the presence of this perfluoroethylene epoxide polyether carboxylic acid's alkali metal salt, can
Exemplify vinylidene fluoride, tetrafluoroethene, hexafluoropropene, CTFE, trifluoro-ethylene, fluorothene, to have carbon number be 1
The perfluor (alkyl vinyl ether) etc. of the alkyl of ~ 3, one kind or two or more by for polyreaction, shape in these fluorochemical monomers
Become homopolymer or copolymer.These fluorochemical monomers can also form copolymer with not fluorochemical monomer, such as propylene, ethylene etc..
When carrying out polyreaction, this perfluoroethylene epoxide polyether carboxylic acid's alkali metal salt as required can with other known to
Fluorine system emulsifying agent is together as the emulsifying agent (and copolymer composition) during emulsion polymerization, with relative to the addition of water or water solublity
The aqueous medium of alcohol etc. is about 0.03 ~ 2 weight %, the preferably from about ratio of 0.1 ~ 1 weight % and uses.Polyreaction is preferably at water
Carry out in the presence of soluble polymerization initiator or draw being polymerized of redox system defining with water-soluble polymerization initiator
Sending out in the presence of agent and carry out, gained reactant mixture can make it by being added to aqueous metal salts such as calcium chloride etc.
Condensation, and make it wash, be dried, thus obtain with the homopolymer of desired fluorochemical monomer or the form of copolymer.
Then, for embodiment, the present invention is described.
Embodiment 1
Use ice and salt, 2 will conventionally prepared, 3,3,3-tetra-fluoro-2-(1,1,2,2-tetra-fluoro-2-(1,2,2-trifluoro
Ethyleneoxy) ethyoxyl) methyl propionate CF2=CFO(CF2)2OCF(CF3)COOCH3(a=2, b=0, c=0) 5.19g (13.3 mmoles
You) ethanol solution 5ml be cooled to less than-10 DEG C.Then, drip lentamente using-10 DEG C as the upper limit and make potassium hydroxide (pure
Spend 85 weight %, 0.9g) it is dissolved in the ethanol solution (concentration 15.8 weight %) cooling down ethanol 5ml and obtain.After they 8 hours,
When removing ethanol with Rotary Evaporators, obtain wax-like white solid 4.90g.
1The result that H-NMR measures, the blackout of display methyl ester,19During F-NMR measures ,-CF (CF3)-methine
Signal is subjected to displacement, therefore, it is judged that obtained 2,3,3,3-tetra-fluoro-2-(1,1,2,2-tetra-fluoro-2-(1,2,2-trifluoro-ethylene oxygen
Base) ethyoxyl) potassium propionate.
Embodiment 2
Use ice and salt, 2 will conventionally prepared, 3,3,3-tetra-fluoro-2-{1,1,2,3,3,3-hexafluoro-2-(1,1,2,
The fluoro-2-of 2-tetra-(trifluoro-ethylene epoxide) ethyoxyl) propoxyl group } methyl propionate CF2=CFO(CF2)2OCF(CF3)CF2OCF(CF3)
COOCH3(a=2, b=0, c=1) and the fluoro-2-{1,1,2,2-of 2,3,3,3-tetra-tetra-fluoro-2-(1,2,2,3,3,3-hexafluoro-2-(three
Fluorothene epoxide) propoxyl group) ethyoxyl } methyl propionate CF2=CFOCF2CF(CF3)O(CF2)2OCF(CF3)COOCH3 (a=2、b=
1, c=0) the ethanol solution 8ml of mixture 10.8g (20.0 mMs) be cooled to less than-10 DEG C.Then, using-10 DEG C as
The ethanol solution that the upper limit and being slowly added dropwise makes potassium hydroxide (purity 85 weight %, 1.32g) be dissolved in cooling ethanol 10ml and obtains
(concentration 12.5 weight %).After they 8 hours, when removing ethanol with Rotary Evaporators, obtain wax-like white solid 9.88g.
1The result that H-NMR measures, the blackout of display methyl ester,19During F-NMR measures ,-CF (CF3)-methine
Signal is subjected to displacement, therefore, it is judged that obtained 2,3,3,3-tetra-fluoro-2-{1, and (1,1,2,2-tetra-is fluoro-for 1,2,3,3,3-hexafluoro-2-
2-(trifluoro-ethylene epoxide) ethyoxyl) propoxyl group } potassium propionate and the fluoro-2-of the fluoro-2-{1,1,2,2-of 2,3,3,3-tetra-tetra-(1,2,2,
3,3,3-hexafluoro-2-(trifluoro-ethylene epoxide) propoxyl group) ethyoxyl } mixture of potassium propionate.
Reference example
In the pressure vessel made from stainless steel of internal volume 10L with stirring vane, put into:
CF3CF2CF2〔OCF(CF3)CF2〕OCF(CF)3COONH4(emulsifying agent) 34g
CF2=CFO(CF2)2OCF(CF3) COOK (reactive emulsifier) 2.4g
Na2HPO412 hydrates (buffer agent) 17g
I(CF2)4I (chain-transferring agent) 27g
Ion exchange water 5600g
Then, carry out nitrogen and replace the oxygen removing in reactor, put into wherein:
Perfluor (methyl vinyl ether) CF2=CFOCF3〔PMVE〕 790g
Vinylidene fluoride (VdF)/tetrafluoroethene (TFE) 670g
Mixed gas (VdF/TFE=87.5 mole of %/12.5 mole %).
The temperature in reactor is made to be warming up to 50 DEG C.Reactor pressure when reaching 50 DEG C is 3.07MPaG.Confirm temperature
After Wen Ding, it is added to the Ammonium persulfate. 0.8g and sodium sulfite 0.2g of aqueous solution form, starts polyreaction.
Carrying out polyreaction, when the pressure in reactor reaches 3.00MPaG, importing mixing ratio is VdF/TFE/PMVE
The monomer mixture of=79.6/11.4/9.0 mole of %, boosts to 3.10MPaG.By importing above-mentioned composition in the polymerization
Gas, the pressure in reactor is remained 3.00 ~ 3.10MPaG.
Stop when the gas gross imported reaches 1410g dividing adding, reach the moment cooling reaction of 0.20MPaG at pressure
Device, stops polyreaction.Time required stopping to polymerization from putting into initiator is 288 minutes.After reaction terminates, with
The form of reactant mixture obtains the fluoroelastomer latex of 8550g.
Gained fluoroelastomer latex is put into after making latex agglutination to 1 weight % calcium chloride water of equivalent, carry out
Filter and utilize the ion exchange water of 5 times amount to clean 5 times, utilizing vacuum desiccator to be dried, obtain the VdF/TFE/ of 2500g
PMVE copolymer.By19The measurement result of F-NMR confirms: gained copolymer is following such composition.
73.6 moles of % of VdF
9.5 moles of % of TFE
16.9 moles of % of PMVE
CF2=CFO(CF2)2OCF(CF3) 0.03 mole of % of COOK
Coordinate in gained copolymer 1 00 weight portion:
MT carbon black 37 weight portion
Triallyl isocyanurate (Japan chemical conversion goods TAIC WH60) 4 〃
Organic peroxide (day oil product パ ヘ キ サ 25B-40) 1.5 〃.
Use mill carry out mixing prepare unvulcanized blank after, carry out the press cure of 6 minutes with 180 DEG C, and with
230 DEG C of baking oven sulfurations carrying out 22 hours, carry out the normality physical property of gained sulfide (according to the JIS corresponding with ISO 48
K6253 and the JIS K6251 corresponding with ISO 37) and Compression Set (the JIS K6262 according to corresponding with ISO 815)
Mensuration.
It addition, after the unvulcanized blank that zinc phosphate processes before engaging press cure on SPCC steel plate, carry out 6 with 180 DEG C
Minute pressurization crosslinking make fluoroelastomer stacking metallic plate, for this fluoroelastomer stacking metallic plate, carry out 90 ° of strippings
Separating test (the JIS K6256 according to corresponding with ISO 813).
Comparison reference example 1
In reference example, do not use the CF in emulsifier component2=CFO(CF2)2OCF(CF3) COOK, obtain VdF/TFE/PMVE
Copolymer.
The result obtained in above reference example and comparison reference example 1 is as shown in the table.
Comparison reference example 2
Processing on SPCC surface of steel plate at zinc phosphate, it is bonding that coating makes using amino silane and vinyl silanes as main component
Agent (ロ De company goods ケ system ノ ッ Network AP-133) is dissolved in the butanone of 4 times amount and the solution that obtains, at ambient temperature
After being dried 30 minutes, with 150 DEG C of enforcement baking of 30 minutes.Joint comparison reference it is formed on the metallic plate of bond layer at this
Unvulcanized blank before the press cure prepared in example 1, cross-links with 180 DEG C of pressurizations carried out 6 minutes, thus makes fluorine-containing elasticity
Body laminated metal plate.For this fluoroelastomer stacking metallic plate, when similarly carrying out 90 ° of disbonded tests, peel strength is 1.1
(N/mm)。
Industry applications
Perfluoroethylene epoxide polyether carboxylic acid's alkali metal salt of the present invention has high polymerization, therefore can effectively serve as various
The cross-linking agent of polymer, modification agent, additionally have a high Oil repellent, therefore, not only can improve or improve and employ the various of its
The thermostability of polymer, weatherability, chemical reagent resistance etc., also show low-refraction, therefore can be additionally used in the anti-of display etc.
Reflectance coating, the clad material etc. of optical fiber.
And then, terminal carbonyl is polar functional group, therefore when for bonding agent purposes, it is possible to realize relative to various portions
The raising of the cementability of part, it addition, also have surface active properties, therefore, it may also be used for various demoulding coating agents, surface-coated
The purposes such as agent, surface modifier, water-repellent oil-repellent agent.
Claims (7)
1. perfluoroethylene epoxide polyether carboxylic acid alkali metal salt, it uses formula CF2=CF〔OCF2CF(CF3)〕bO(CF2)aO〔CF(CF3)
CF2O〕cCF(CF3) COOM (I) expression,
Herein, M is alkali metal, and a is the integer of 1 ~ 6, and b+c is the integer of 0 ~ 6.
Perfluoroethylene epoxide polyether carboxylic acid's alkali metal salt the most according to claim 1, wherein, alkali metal is sodium or potassium, and a is
2, b+c is 0 or 1.
3. the manufacture method of perfluoroethylene epoxide polyether carboxylic acid alkali metal salt, described perfluoroethylene epoxide polyether carboxylic acid's alkali metal salt
Use formula CF2=CF〔OCF2CF(CF3)〕bO(CF2)aO〔CF(CF3)CF2O〕cCF(CF3) COOM (I) expression, herein, M is alkali
Metal, a is the integer of 1 ~ 6, and b+c is the integer of 0 ~ 6, and described manufacture method is characterised by,
Make formula CF2=CF〔OCF2CF(CF3)〕bO(CF2)aO〔CF(CF3)CF2O〕cCF(CF3) the perfluor second shown in COOR (II)
Alkenyloxy group polyether carboxylic acid's Arrcostab is hydrolyzed or solvolysis in the presence of an alkali metal hydroxide,
Herein, R is the alkyl of carbon number 1 ~ 12, and a is the integer of 1 ~ 6, and b+c is the integer of 0 ~ 6.
The manufacture method of perfluoroethylene epoxide polyether carboxylic acid's alkali metal salt the most according to claim 3, wherein, with relative to
Perfluoroethylene epoxide polyether carboxylic acid's Arrcostab is that the ratio of 0.95 ~ 1.05 times mole uses alkali metal hydroxide.
The manufacture method of perfluoroethylene epoxide polyether carboxylic acid's alkali metal salt the most according to claim 3, wherein, alkali metal hydrogen
Oxide is sodium hydroxide or potassium hydroxide.
The manufacture method of perfluoroethylene epoxide polyether carboxylic acid's alkali metal salt the most according to claim 3, wherein, for solvent
The aliphatic alcohol that solvent is carbon number 1 ~ 6 decomposed.
The manufacture method of perfluoroethylene epoxide polyether carboxylic acid's alkali metal salt the most according to claim 3, wherein, by entirely
Alcoholic solution in the water-based emulsion of fluorothene epoxide polyether carboxylic acid's Arrcostab or drips aqueous solution or the alcohol of alkali metal hydroxide
Solution, thus be hydrolyzed or solvolysis.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2014-003434 | 2014-01-10 | ||
| JP2014003434 | 2014-01-10 | ||
| PCT/JP2014/083709 WO2015104977A1 (en) | 2014-01-10 | 2014-12-19 | Alkali metal salt of perfluoro(vinyloxy polyether) carboxylic acid, and method for producing same |
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| CN105873894A true CN105873894A (en) | 2016-08-17 |
| CN105873894B CN105873894B (en) | 2017-11-07 |
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| US (1) | US9765008B2 (en) |
| EP (1) | EP3093281B1 (en) |
| JP (1) | JP5783345B1 (en) |
| CN (1) | CN105873894B (en) |
| WO (1) | WO2015104977A1 (en) |
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- 2014-12-19 US US15/110,579 patent/US9765008B2/en active Active
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- 2014-12-19 WO PCT/JP2014/083709 patent/WO2015104977A1/en active Application Filing
- 2014-12-19 CN CN201480072771.XA patent/CN105873894B/en active Active
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| KUNIAKI TAKATA ET AL.: "Synthesis of vinyl ether compounds by pyrolysis of dimethyl perfluoro2,7-dimethyl-3,6-dioxa- 1,8-octanedioate", 《JOURNAL OF FLUORINE CHEMISTRY》 * |
Also Published As
| Publication number | Publication date |
|---|---|
| US9765008B2 (en) | 2017-09-19 |
| JPWO2015104977A1 (en) | 2017-03-23 |
| EP3093281A4 (en) | 2017-06-07 |
| EP3093281A1 (en) | 2016-11-16 |
| JP5783345B1 (en) | 2015-09-24 |
| US20160332951A1 (en) | 2016-11-17 |
| EP3093281B1 (en) | 2018-11-21 |
| WO2015104977A1 (en) | 2015-07-16 |
| CN105873894B (en) | 2017-11-07 |
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